Base oils and methods of making the same

ABSTRACT

A process for the preparation of saturated hydrocarbon base oils is provided, comprising oligomerization of a feed mixture that has an average carbon number in the range of 14 to 18 to produce an oligomer product comprising dimers, trimers, and higher oligomers, where the dimer has a branching proximity (BP) of 20 or greater, isomerization of at least the dimer portion, and hydrogenation of the isomerized product. The dimer portion is separated from the oligomer product, and a saturated hydrocarbon base oil is obtained comprising greater than 90% dimers having an average carbon number in the range of from 29 to 36, and the dimer portion having a weight average molecular weight in the range of 422 to 510, where the dimers have an average Branching Index (BI) in a range of 22 to 26 and an average paraffin branching proximity (BP) in a range of from 18 to 26.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 16/630,324 filed on Jan. 10, 2020, now U.S. Pat. No.11,332,690, which is a national stage application of PCT/US2018/041993,filed Jul. 13, 2018, claims priority to U.S. provisional application No.62/532,773, filed on Jul. 14, 2017, the entire contents of the each ofwhich is hereby incorporated by reference herein as if recited in fullherein.

FIELD OF THE INVENTION

Aspects of present disclosure generally relate to synthetic hydrocarbonbase oils. Described herein are isoparaffin oligomers derived fromalpha-olefins and/or linear internal olefins with improved lowtemperature properties by catalytic isomerization of the oligomers. Theresulting product may be capable of providing an excellent lubricantbase oil.

BACKGROUND

The automotive industry is placing greater demands on engine oils,operating at higher temperatures for longer times and requiring lowerviscosity engine oil formulations such as OW-30 and OW-20 engine oils.These lower weight engine oils improve vehicle fuel economy by loweringfriction losses. This desire for lower weight engine oils is driving ademand for low viscosity PAOs, such as those around 4 cSt kinematicviscosity. Allowing for engine oils with decreased viscosity whilemaintaining low Noack volatility and good low-temperature performanceproperties.

Poly Alpha Olefins (PAOs) and Poly Internal Olefins (PIOs) make upimportant classes of hydrocarbon lubricating oils. They are typicallyproduced by the polymerization of alpha-olefins or internal-olefins inthe presence of a Friedel Crafts catalyst such as AlCl₃, BF₃, or BF₃complexes. For example, 1-octene, 1-decene, 1-dodecene, and1-tetradecene have been used to manufacture PAOs. C8-C18 internalolefins have been used to manufacture PIOs. Fractionation andhydrogenation typically follow oligomerization of the olefins to removeany remaining unsaturated monomer moieties.

The poly alpha olefin products are typically obtained with a wide rangeof viscosities varying from low molecular weight and low viscosity ofabout 2 cSt at 100° C., to higher molecular weight, viscous materialswhich have viscosities exceeding 100 cSt at 100° C. The poly alphaolefins may be produced by the polymerization of olefin feed in thepresence of a catalyst, such as, AlCl₃, and BF₃ complexes. Processes toproduce poly alpha olefin lubricants are disclosed, for example, in U.S.Pat. Nos. 3,382,291; 4,172,855; 3,742,082; 3,780,128; 3,149,178;4,956,122; and 5,082,986. Poly alpha olefins and poly internal olefinslubricants are discussed in Synthetic Lubricants and High-PerformanceFunctional Fluids, Revised and Expanded. Edited by Leslie R. Rudnick andRonald L. Shubkin CRC Press 1999. The polymerization reaction istypically conducted in the absence of hydrogen; the lubricant rangeproducts are thereafter polished or hydrogenated to reduce the residualunsaturation.

Prior efforts to prepare various PAOs that can meet the increasinglystringent performance requirements of modern lubricants and automotiveengine oil particularly have favored low viscosity polyalphaolefin baseoils derived from 1-decene alpha-olefins, alone or in some blend withother mineral, or Fischer-Tropsch derived base oils. However, thepolyalphaolefins derived from 1-decene can be prohibitively expensiveand its supply is limited. Thus, a need exists for low viscosity baseoils which are made from olefins other than 1-decene and that exhibitproperties such as relatively low Noack volatility, calculated accordingto ASTM D 5800 Standard Test Method for Evaporation Loss of LubricatingOils by the Noack Method, low cold-crank viscosity (i.e. dynamicviscosity according to ASTM D 5293, CCS), and/or additional SAE OW lowtemperature viscometric requirements.

The properties of a particular grade of PAO are typically dependent onthe alpha olefin feedstock used to make that product. Commercially, someC28 to C36 oligomers of alpha olefins are made from a mixed feed of C8,C10 and C12 alpha olefins, with 1-decene being incorporated for thepurpose of imparting the most desirable properties.

In contrast, 4 cSt PAOs and PIOs made without decene have yielded baseoils lacking in one or more important physical properties (e.g.,viscosity index, Noack volatility, and low temperature CCS). Thus, PAOsmade from C8 through C12 mixed alpha-olefin feeds, such as the C28 toC36 oligomers may have the advantage that they lower the amount ofdecene that is needed to impart predetermined properties. However, theystill do not completely remove the requirement for providing decene as apart of the oligomer, in order to impart the appropriate physicalproperties. Therefore, there is a need for products that incorporatealpha olefins other than C8, C10 and C12, to make polyolefin base oils.

Poly internal-olefins (PIOs) are typically produced by thepolymerization of internal-olefins in the presence of a Friedel Craftscatalyst such as AlCl₃, BF₃, or BF₃ complexes. C8-C18 internal olefinshave been used to manufacture PIOs. Oligomerization of these olefins istypically followed by fractionation and hydrogenation to remove anyremaining unreacted hydrocarbons and unsaturated moieties. Such PIOshave been prepared with properties including 4.33 cSt viscosity at 100°C., 20.35 Vis at 40° C., 122 Viscosity Index, pour point of −51° C. andNoack volatility of 15.3 (Data taken from Synthetic Lubricants andHigh-Performance Functional Fluids, Revised and Expanded. Edited byLeslie R. Rudnick and Ronald L. Shubkin CRC Press 1999.) This producthas excellent low pour point, but the VI is too low, and the NoackVolatility too high, for modern OW engine oils. Therefore, a need for anon-1-decene based polyolefin exists in the market.

Other examples of processes for making PIOs can be found, for example,in EP 1,104,747, EP 0,776,960, and U.S. Pat. No. 4,910,355.

Furthermore, conventional processes to make these PAOs and PIOs may alsoresult in the production of significant quantities of cross-oligomersthat do not have the desired properties for a 4 cSt base oil.Accordingly, narrow distillation cuts must typically be taken to selectonly the oligomers having the desired properties, resulting inundesirably low yields of functional product.

Therefore, there remains a need for a base oil composition havingproperties within commercially acceptable ranges for physical propertiesincluding one or more of the viscosity, Noack volatility, and lowtemperature cold-cranking viscosity, for use for example in automotiveand other applications. Furthermore, there remains a need for base oilcompositions having improved properties and methods of manufacturethereof, where the base oil compositions have reduced amounts of1-decene incorporated therein, and may even preferably eliminate the useof 1-decene in the manufacture thereof.

Large quantities of poly alpha olefins are used in a variety oflubricating applications. However, PAOs existing in the market today arederived from fossil fuels. Another potential source for makingpolyolefin base oils is from renewable sources. Therefore, it isdesirable to produce base oils and PAOs from renewable sources. Alphaolefins can be made via dehydration of a fatty alcohol.

Naturally occurring sources of said renewable alcohols do not have highconcentration of C8-C12 length alcohols, and instead have a highconcentration of alcohols in the range of C14-C18. Previous attempts touse linear alpha olefins in the C14-C18 range, without 1-decene, madepoly alpha olefins with unacceptably high pour points lubricants, i.e.higher than −24° C., that are unsuitable for use in a variety ofdifferent lube oils, including OW engine oils. High pour points increasethe cold-cranking viscosity at −35° C. (ASTM D5293-02). Accordingly,there is a need for polyolefins with low enough pour points that thecold-cranking viscosities are suitable for OW engine oils, whileexhibiting volatilities that are acceptable.

Up to now, however, commercially successful poly alpha olefin base oilshave been limited to those comprising C8, C10 and C12 linearalpha-olefins. No commercial process has been demonstrated to convertother olefins to polyolefins with advantageously low pour points, CCS at−35° C. and low Noack volatility properties for PAO based lubricantoils. Aspects of the present disclosure are directed to overcoming thisand other deficiencies in the art.

SUMMARY OF THE INVENTION

Aspects of the present disclosure relate to a process for themanufacture of branched saturated hydrocarbons, which may be suitablefor use as synthetic base oils or base oil components. In accordancewith aspects of the present disclosure, a new alternative process hasbeen discovered for producing polyolefin base oils from olefins, such asfrom alpha-olefins, or mixtures of alpha and internal-olefins, as wellas optionally internal-olefins. C14 to C18 alpha or internal-olefins areused in this process as the primary feedstocks for oligomermanufacturing, thereby easing the demand for high price 1-decene andother crude oil or synthetic gas based olefins as feedstocks, and makingavailable alternate sources of olefin feedstocks such as those derivedfrom C14-18 alcohols. Provided herein are also base oils and lubricantcompositions derived from one or more olefin co-monomers, where saidolefin co-monomers are oligomerized to dimers, trimers, and higheroligomers. In a preferred embodiment, the process according to aspectsof the disclosure isomerizes at lease the dimer portion of theoligomers. The resulting dimers have excellent pour point, volatilityand viscosity characteristics and additive solubility properties.

Briefly, in a first aspect of the present disclosure, a process forpreparing a C14 to C18 olefin oligomer with excellent low temperatureproperties is provided, comprising: forming a reaction mixture of anoligomerization catalyst system and a C14 to C18 olefin monomer feedmixture, polymerizing the olefin monomer feed in the reaction mixture toproduce an oligomer product. In one embodiment, the dimer portionproduced by the oligomerization has a branching proximity of 20 orgreater. At least the dimer portion of the oligomerization product isisomerized in the presence of an acid catalyst. The isomerized oligomerproduct is hydrogenated, and the dimer fraction can be separated, suchas by distillation, such that a polyolefin lubricant compositioncomprising an average carbon number in the range of C29-C36 is obtained.In one embodiment, the resulting polyolefin base oil may have a weightaverage molecular weight between 422 and 510, and pour point of −27° C.or below, having a kinematic viscosity at 100° C. in the range of fromabout 3.7 to about 4.8 cSt, with a branching index (BI) greater than 22,but less than 26, a Noack weight loss in the range of from about 6 toabout 14%, and a viscosity index greater than 124.

Other aspects, features and embodiments of the present disclosure areprovided in the following description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram illustrating a process embodiment including: a1-stage and optionally a 2-stage oligomerization reaction, recycling ofthe unreacted monomer back into the 1st stage of the oligomerizationprocess, hydrogenation of the oligomers, and fractional distillation toseparate the oligomers into 1 or even 2 base oil distillate cuts (a andb bottoms product).

FIG. 2 shows a block diagram showing a process embodiment including thepreparation of an internal olefin feedstock by the catalyticisomerization of a linear alpha olefin, and the optional distillation ofan unsaturated monomer co-product.

FIG. 3. Carbon labeling representation for a representative example ofisomers of a GTL C30H62 paraffin used for lubricant applications.

FIG. 4. Representative example of 1-Decene trimer 4 cSt PAO.

FIG. 5. Representative example of a 4 cSt base oil typical of aisodewaxed oils or Gas to liquids (GTL) base oils.

FIG. 6. The reaction process for a representative example of anisomerized 4 cSt 1-tetradecene and 1-hexadecene 4 cSt Dimer.

FIG. 7. Branching index (BI) for an embodiment of a hydrogenated1-tetradecene and 1-hexadecene dimer 4 cSt polyolefin lube oil madewithout isomerization.

FIG. 8. Embodiments of isomerization and hydrogenation of C14 and C16olefins dimers.

FIG. 9. Illustrates an embodiment of oligomerization of alpha olefins,followed by either (A) both isomerization followed by hydrogenation ofthe oligomer product, or (B) hydrogenation alone.

DETAILED DESCRIPTION

According to aspects of the disclosure, olefin oligomers are obtained byproviding at least one C14-C18 olefin monomer, or a mixture of two ormore of said olefin monomers (e.g., as shown in box 1 of FIGS. 1 and 2).The olefin monomer can also be prepared by providing linear or branchedalpha olefins (such as C14-C18 branched alpha olefin monomers), oroptionally a linear or branched internal olefin. The olefin monomer isoligomerized, for example either with itself, or with a second olefin(e.g., as shown in boxes 2a-2c of FIGS. 1 and 2), which may be aninternal olefin monomer having a different chain length and/or differentaverage double bond position, and/or may be a C14 to C18 alpha olefinmonomer, such as a linear alpha-olefin monomer. In one embodiment, whereone of the olefin monomers used to form the oligomer is a C14 alphaolefin monomer, the other olefin monomer may have a chain length greaterthan C14. For example, if a C14 linear alpha olefin monomer is used asthe first olefin, the second olefin monomer may comprise a C15 to C18linear alpha olefin monomer. In the process embodiment shown in FIG. 1,one or more olefin feeds (e.g., Olefins 1, 2 and 3 in boxes 2a-2c), arecombined together to form the olefin mixture in box 1, where the one ormore olefin feeds can comprise alpha olefins, and/or may in certainembodiments comprise internal olefins. In the process embodiment shownin FIG. 2, at least one of the olefin feeds is subjected to anisomerization process to result in an isomerized olefin (e.g., OlefinIsomerization in box 2b) having an isomerized double bond position, andthis isomerized olefin feed can be optionally combined with anotherolefin feed (e.g., Olefin 1 in box 2), to provide the olefin mixture inbox 1. The olefin mixture of box 1 may be exposed to Boron Trifluorideand an alcohol or ester promoter in an oligomerization stage, as shownin boxes 3 and 5 of FIGS. 1 and 2, to form an oligomer from the olefinmonomer mixture in reaction vessel shown in box 1 of FIGS. 1 and 2.Optionally a second stage reactor can be used to further react theolefin mixture under different reaction conditions as shown in box 5 ofFIGS. 1 and 2, and may provide a dimer portion of the oligomer productthat has a branching proximity of 20 or greater. The BF₃ promotor adductmay be separated and recycled back to the oligomerization reactor asshown in box 6 of FIGS. 1 and 2. The unreacted monomer can be removed,and optionally recycled back into the starting olefin mixture, as shownin box 7 of FIGS. 1 and 2, or collected as an unsaturated co-product. Inone embodiment, the resulting mixture of oligomers is isomerized toincrease the degree of branching as shown in box 8 of FIGS. 1 and 2, andhydrogenated, as shown in box 9 of FIGS. 1 and 2. The dimer fraction maybe separated therefrom, as shown in box 10 to produce a hydrocarbon baseoil with desirable physical properties for use as an engine oil baseoil, such as properties suitable for OW formulations and above, as shownin box 11. A bottoms product may be recovered as shown in box 11suitable as a higher viscosity blend stock for engine oil applicationsor a base oil for higher viscosity industrial or other vehiclelubricants. Optionally a saturated or unsaturated lights co-product maybe recovered as shown in box 13. In one embodiment, the resulting dimermay have a KV100 between 3.7 and 4.8 cSt, with a viscosity index of 125or greater, with a pour point between −27° C. and −45° C., with a CCS at−35 C of less than 1800 cP, and a Noack volatility of less than 14%.

Aspects of the present disclosure relate to a method for makingsaturated C28-C36 hydrocarbons useful for engine oil applications. Inone embodiment, olefins ranging from 14 to 18 carbons in size areexposed to a strong Lewis acid catalyst such as BF₃ coupled with apromoter molecule. According to one embodiment, the unreacted monomer isdistilled off, and the resulting oligomers are further isomerized in theabsence of hydrogen. The dimers may be separated by distillation, andhave ideal properties for use in an engine oil formulation, with arelatively high VI, low CCS, low Noack, and low Pour Point.

Feedstock Selection

In one embodiment, a feed alpha olefin, such as C14 to C18, can beeither an alpha olefin, or may be an olefin feed that has been producedby isomerizing an alpha olefin to form an internal olefin prior tooligomerization, via selective internal isomerization of the α-olefinusing a catalyst (which may be an inexpensive catalyst), and underisomerization conditions that may inhibit olefin deterioration and sidereactions, such as skeletal isomerization, oligomerization, andcracking.

Aspects of the disclosure relate to the surprising discovery that anoligomer derived from C14-C18 alpha olefins and/or internal olefins canhave the desired viscosity, Noack volatility, and/or low temperature COSviscosity, such as values of these properties that are withincommercially preferred ranges. According to aspects of the disclosure,by controlling the oligomerization reaction conditions and the degree ofbranching through isomerization of the oligomers, a mixture of C14-C18olefins, such as olefins selected from the group consisting of1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene,(and/or optionally branched structural isomers of these olefins) and/orinternal olefins derived from linear internal or branched internalpentadecenes, hexadecenes, heptadecenes and octadecenes, can producedimers offering excellent low temperature performance, high viscosityindex, and low volatility. In one embodiment, the olefin monomers of thefeed mixture may be selected from the group consisting of unsaturated,linear alpha-olefins, unsaturated, linear internal olefins, branchedalpha olefins, branched internal olefins, and combinations thereof. Inyet another embodiment, the olefin monomers of the feed mixture maycomprise a mixture of linear alpha olefins and/or linear internalolefins. According to certain embodiments, the longer linear paraffinbranches produced from C14-C18 olefins increases the VI and reduce theCCS of the oligomers, while the pour point of the oligomers can bereduced by the introduction of branching through isomerization of thedimer.

In one embodiment of the disclosure, the feedstocks used to form theoligomers are C14 to C18 olefins comprising less than 36% by weight ofbranched olefins. In yet another embodiment, the feedstock used to formthe oligomers are C14 to C18 olefins comprise less than 20% by weight ofbranched olefins monomers. In yet another embodiment, the feedstocksused to form the oligomers are C14 to C18 olefins comprise less than 10%by weight of branched olefins. In yet another embodiment, the feedstockused to form the oligomers are C14 to C18 olefins comprise less than 5%by weight of branched olefins.

Furthermore, in one embodiment, an amount of decene in the feedstockmixture is less than 20% by weight. In yet another embodiment, an amountof decene in the feedstock mixture is less than 10% by weight. In yetanother embodiment, an amount of decene in the feedstock mixture is lessthan 5% by weight. In yet another embodiment an amount of decene in thefeedstock mixture is less than 1% by weight.

In some variations, about 100% of the carbon atoms in the olefinfeedstocks described herein originate from renewable carbon sources. Insome variations, about 100% of the carbon atoms in the olefin co-monomeroriginate from renewable carbon sources. For example, an alpha-olefinco-monomer may be produced by oligomerization of ethylene derived fromdehydration of ethanol produced from a renewable carbon source. In othervariations, at least 90%, and even at least 95% of the carbon atoms inthe renewable feedstocks originate from renewable carbon sources.

In some variations, alpha olefin monomers may be produced by dehydrationof a primary alcohol other than ethanol that is produced from arenewable carbon source. In one embodiment, the C14 to C18 alpha olefinmonomers used as feedstocks for the oligomerization are derived from thedehydration of C14 to C18 primary alcohols selected from the groupconsisting of 1-tetradecanol, 1-pentadecanol, 1-hexadecanol,1-heptadecanol, and 1-octadecanol. In yet another embodiment, C14 to C18primary alcohols are converted to the C14 to C18 alpha olefin monomers,and isomerized to form the isomerized C14 to C18 olefin monomer of thefeed-stock product by exposure to a di-functional catalyst (e.g., acatalyst capable of both dehydrating the primary alcohols to form alphaolefin monomers, and isomerizing the alpha-olefin monomers to internalolefins).

In some embodiments, hydrocarbon terpene feedstocks derived fromrenewable resources are coupled with one or more olefins that arederived from renewable resources.

Oligomerization Process

According to one embodiment of the process of forming the oligomercomposition, an alpha olefin [e.g., 1-tetradecene] is either mixed withan alpha or internal olefin [e.g. 3-hexadecene internal olefin], orpolymerized solely (i.e. with itself) by either by semi-batch orcontinuous mode in a single stirred tank reactor, and/or by continuousmode in a series of stirred tank reactors using catalysts such as BF₃and/or BF₃ promoted with a mixture of linear alcohol and an alkylacetate ester.

In one embodiment, the oligomerization reaction conditions arecontrolled to impart a defined amount of isomerization, and to producean at least partially branched unsaturated oligomer. That is, theoligomerization process conditions may be selected to not onlyoligomerize, but also at least partially isomerize, with theisomerization being controlled to a predetermined extent to avoidexcessive branching of the dimer product at the oligomerization stage.In one embodiment, any isomerization occurring during oligomerization iscontrolled such that the dimer product resulting from theoligomerization has an average branching proximity (BP), of 20 orgreater, and even 22 or greater. The branching proximity is a measure ofthe % equivalent recurring methylene carbons in the dimers, which arefour or more removed from a carbon end group or branching carbon group(e.g., the epsilon carbons as shown in FIG. 3), and may be determinedaccording to the following formula:

paraffin branching proximity (BP)=(number of ε carbon groups/totalnumber of carbon groups)*100,

where an ε carbon group is defined as a carbon group that is separatedfrom any terminal carbon atom groups or branching carbon groups by atleast 4 carbon groups. That is, higher branching proximities mayindicate a more linear molecule and/or longer hydrocarbon chains betweenbranches (e.g., more recurring methylene carbons), whereas lowerbranching proximities may indicate more branching in the molecule and/orshorter hydrocarbon chains between branches (e.g., fewer recurringmethylene carbons). Note that the branching proximity (BP) is typicallymeasured for a saturated compound, and thus any calculation of branchingproximity of the dimer product produced in the oligomerization stepwould involve hydrogenation of the dimer product prior to branchingproximity (BP) measurement. That is, in order to determine the branchingproximity (BP) of the dimers produced in the oligomerization processitself (i.e., without any subsequent isomerization), the dimers may behydrogenated to a Bromine Index below 1000 mg Br₂/100 g as determined inaccordance with ASTM D2710-09. However, as described in further detailbelow, in preparing a base oil comprising dimers according to aspects ofthe present disclosure, the oligomerized dimer product may be subject tofurther isomerization post-oligomerization, and prior to hydrogenation,to achieve the product. That is, while hydrogenation of the oligomerizeddimers can be performed for the purposes of determining the branchingproximity (BP) achieved after an oligomerization process, embodiments ofthe disclosure provide that a final saturated hydrocarbon base oil isprepared by performing hydrogenation only after a subsequentisomerization process post-oligomerization has been performed.

In one embodiment, the mixture of C14 to C18 olefin monomers areoligomerized in the presence of BF₃ and/or BF₃ promoted with a mixtureof an alcohol and/or an ester, such as a linear alcohol and an alkylacetate ester, using a continuously stirred tank reactor with an averageresidence time of 60 to 400 minutes. In another embodiment, the C14 toC18 olefin monomers are oligomerized in the presence of BF₃ and/orpromoted BF₃ using a continuously stirred tank reactor with an averageresidence time of 90 to 300 minutes. In yet another embodiment, the C14to C18 olefin monomers are oligomerized in the presence of BF₃ and/orpromoted BF₃ using a continuously stirred tank reactor with an averageresidence time of 120 to 240 minutes. A temperature of theoligomerization reaction may be in a range of from 10° C. to 110° C.

Suitable Lewis acids catalysts for the oligomerization process includemetalloid halides and metal halides typically used as Friedel-Craftscatalysts, e.g. AlCl₃, BF₃, BF₃ complexes, BCl₃, AlBr₃, TiCl₃, TiCl₄,SnCl₄, and SbCl₅. Any of the metalloid halide or metal halide catalystscan be used with or without a co-catalyst protic promoter (e.g. water,alcohol, acid, or ester). In one embodiment, the oligomerizationcatalyst is selected from the group consisting of zeolites,Friedel-Crafts catalysts, Bronsted acids, Lewis acids, acidic resins,acidic solid oxides, acidic silica aluminophosphates, Group IVB metaloxides, Group VB metal oxides, Group VIB metal oxides, hydroxide or freemetal forms of Group VIII metals, and any combination thereof.

In one embodiment, the reaction mixture is distilled to remove theunreacted monomer. For example, the unreacted monomer may be separatedfrom the oligomer product, such as via distillation, and can be recycledback into the mixture of the first and/or second feedstocks foroligomerization thereof. According to one aspect of the presentdisclosure, the unsaturated monomer free oligomer may be furtherisomerized without cracking in the absence of hydrogen, such as viaisomerization in the presence of a catalyst.

Proper control of the oligomerization reaction conditions may beprovided to ensure at least the dimer portion of the oligomers does notbecome too branched. In one embodiment, dimers resulting fromoligomerization of C14-C18 olefins will have an average branchingproximity (BP) of 20 or greater per 100 carbons. For example, if thedimers resulting from the oligomerization were to be hydrogenated to aBromine Index below 1000 mg Br₂/100 g as determined in accordance withASTM D2710-09, without a subsequent isomerizing step, the resultinghydrogenated dimers would exhibit an average paraffin branchingproximity (BP) as determined by 13C NMR of 20 or greater per 100carbons. In yet another embodiment, the dimers have an average branchingproximity of 22 or greater. Dimers with lower branching proximity (below20) as a result from isomerization during oligomerization may notmaintain the necessary amount of linearity after the subsequentisomerization, and thus may exhibit excessive branching of the finaldimer product, and a base oil with an excessively low VI (<124) and adynamic viscosity that is undesirably high (>1800 cP).

In another embodiment, the unsaturated oligomer product is fractionatedby distillation to remove the unreacted monomer portion, and the dimersand heavier oligomers are isomerized simultaneously.

Isomerization Process

In one embodiment, the oligomer product is next subjected toisomerization. Isomerization can be achieved either under hydrogenatmosphere (hydroisomerization), or in the absence of hydrogen.Isomerization (either in the presence or absence of hydrogen) canintroduce additional branching through the rearrangement of the oligomermolecular structure, which may be critical to reducing pour point andimproving low temperature fluidity. A hydroisomerization processrequires hydrogen, and typically requires a high pressure and priorcatalyst activation. Accordingly, in certain embodiments a nonhydroisomerization process may be preferred because of the resultingimproved product distribution, product quality, lower capital cost ofprocess equipment, simplicity of operation, and high efficiency.

In one embodiment, any isomerization catalyst that is conventionallyused for isomerization processes may be used. In one aspect, an acidcatalyst for isomerization can be homogeneous acid catalysts, such asAlCl₃, BF₃, halides of Group IIIA, or modified form of these catalysts,or other typical Friedel-Crafts catalysts, such as the halides of Ti,Fe, Zn, and the like. The acid catalyst can also be selected from thegroup consisting of solid metals or metal oxides or their mixture ofGroup IVB, VB, VIB and Group metal oxides or mixed oxides of Group IIAto VA; other mixed metal oxides (such as WO_(x)/ZrO₂ type catalyst),solid natural or synthetic zeolites, and layered material, crystallineor amorphous material of silica, alumina, silicoaluminate,aluminophosphate, aluminum silicophosphate. These solid acidic catalystsmay also contain other Group VIII metals such as Pt, Pd, Ni, W, etc., aspromoters. Generally, it is preferred to use a solid, regenerablecatalyst for process economic reason and for better product quality. Thepreferred catalysts include: ZSM-5, ZSM-11, ZSM-20, ZSM-22, ZSM-23,ZSM-35, ZSM-48, zeolite beta, MCM22, MCM49, MCM56, SAPO-11, SAPO-31,zeolite X, zeolite Y, USY, REY, M41S and MCM-41, WO_(x)/ZrO₂, etc. Thesolid catalyst can be used by itself or co-extruded with other bindermaterial. Typical binder material includes silica, alumina,silicoalumina, titania, zirconia, magnesia, rare earth oxides, etc. Thesolid acidic catalyst can be further modified by Group III metals, suchas Pt, Pd, Ni, W, etc. The modification can be carried out before orafter co-extrusion with binder material. Sometimes the metalmodification provides improvement in activity, sometimes it is notnecessary. An example of discussion of catalysts and their preparationcan be found in U.S. Pat. No. 5,885,438 which is incorporated herein byreference. Furthermore, in one embodiment the catalyst provided duringisomerization is a different catalyst than that provided duringoligomerization, for example to provide for differing extents and typesof isomerization that what may occur during the oligomerization process.

In one embodiment, the acid catalyst provided for isomerizing theunsaturated polyolefin produced in the oligomerization process is azeolite having a Constraint Index of about 2 to about 12. In anotherembodiment, the acid catalyst provided for isomerizing the unsaturatedpolyolefin produced in the oligomerization process is a zeolitecontaining one or more Group VI B to VIII B metal elements.

In one embodiment, the isomerization can be carried out in any of afixed-bed, continuous operation, in batch type operation or incontinuous stir tank operation. Generally, the residence time of theoligomer product under the isomerization conditions (e.g., residencetime in fixed-bed reactor) may range from a few seconds to up to one ortwo days depending on reaction temperature, catalyst activity andcatalyst particle size. For economic reasons, it may be preferred to useshorter residence times, if sufficient isomerization can be achieved togive improved properties. In one embodiment, residence time of 10minutes to 20 hours residence time may be suitable.

In one embodiment, the isomerization is conducted at temperatures in therange of about 200° C. to about 400° C., and preferably at about 225° C.to about 300° C., and at pressures of about 0 kPa to about 13.79 MPa(about 0 psi to about 2,000 psi) and preferably about 35.5 kPa (about 15psi) (atmospheric pressure) to about 6.895 MPa (about 1,000 psi), andeven in a range of from 6.89 kPa (1 psi) to 689 kPa (100 psi). Duringthe isomerization, the hydrocarbon cracking may be minimal, and evenless than <1%, and so overall yield loss may be reduced whilemaintaining desired base oil properties (Vis, VI, CCS at −35 100° C. andPP).

In one embodiment, the pour point of the isomerized product is at least−9° C. less than that of the oligomer product prior to isomerization. Inyet another embodiment, the pour point of the isomerized product is atleast −15° C. less than that of the oligomer product prior toisomerization. In yet another embodiment, the pour point of theisomerized product is at least −21° C. less than that of the oligomerproduct prior to isomerization.

Cracked byproducts, naphthalenes and aromatics compounds can be formedduring the isomerization of the oligomerized olefin. Naphtheniccompounds are cyclic saturated hydrocarbons, also known ascycloparaffins. Naphthenic compounds may contain one ring structure(monocycloparaffins) or two rings (dicycloparaffins) or several rings(multicycloparaffins).

It is preferred that cracked hydrocarbons, naphthalenes and aromaticcompounds are not formed, or are only formed in trivial amounts, duringthe isomerization of polyolefins, as they can adversely affectconversion and properties of the final product, specially viscosityindex (VI), oxidation stability and Noack volatility. In one embodiment,the oligomers formed from C14 to C18 olefin monomers are isomerizedunder conditions wherein the amount of cracked byproducts generatedduring isomerization are less than 10% by weight. In another embodiment,the oligomers formed from C14 to C18 olefin monomers are isomerizedunder conditions wherein the amount of cracked byproducts generatedduring isomerization are less than 5% by weight. In yet anotherembodiment, the oligomers formed from C14 to C18 olefin monomers areisomerized under conditions wherein the amount of cracked byproductsgenerated during isomerization are less than 1% by weight. In yetanother embodiment the isomerized oligomers contain less than 5%naphthalenes by weight. In another embodiment, the isomerized oligomerscontain less than 2.5% naphthalenes by weight. in yet another embodimentthe isomerized oligomers contain less than 1% naphthalenes by weight. Inyet another embodiment, a base oil product comprising the dimers formedby the oligomerization and isomerization, may comprise the crackedbyproducts in a wt % that is the same or less than the amount generatedduring the isomerization. For example, in one embodiment, the base oilcan comprise cracked byproducts generated during isomerization that areless than 10% by weight of the base oil. In another embodiment, the baseoil comprises cracked byproducts generated during isomerization than areless than 5% by weight of the base oil. In yet another embodiment, thebase oil comprises of cracked byproducts generated during isomerizationare less than 1% by weight of the base oil. In yet another embodimentthe base oil contains less than 5% naphthalenes by weight. In anotherembodiment, the contains less than 2.5% naphthalenes by weight. In yetanother embodiment the base oil contains less than 1% naphthalenes byweight.

In one embodiment, the isomerization reaction has a relatively highconversion rate for conversion of dimers to isomerized dimer products.For example, according to one embodiment, a percent yield of isomerizeddimers produced in the isomerization is greater than 90% by weight ofthe dimers. In another embodiment, a percent yield of isomerized dimersproduced in the isomerization is greater than 95% by weight. In anotherembodiment, a percent yield of isomerized dinners produced in theisomerization is greater than 97.5% by weight. In another embodiment, apercent yield of isomerized dimers produced in the isomerization isgreater than 99% by weight.

Hydrogenation Process

In one embodiment, the product of the isomerization process is nexthydrogenated. For example, a palladium on carbon catalyst, or supportednickel, or other well-known hydrofinishing catalysts may be used.Hydrogenation conditions include can include, for example, temperaturesof from about 25° C. to about 400° C., and hydrogen pressure of about 1to about 100 atmospheres. The hydrogenated product generally has a lowbromine index of less than about 1000 as measured by ASTM D2710-0.

As described in further detail below, in one embodiment, theisomerization is followed by hydrogenation of the branched hydrocarbonsproduced in the isomerization process. For example, hydrogenation may beperformed to achieve a hydrogenated product having a bromine index ofless than 1000 mg Br/100 g (ASTM D2710-09). Hydrogenation processes aredescribed in, e.g., see U.S. Pat. Nos. 7,022,784 and 7,456,329, whichare incorporated herein by reference.

In a further embodiment, the oligomer product is hydrogenated to form asaturated oligomer product comprising a mixture of branched saturatedhydrocarbons including hydrogenated dimer, trimer, and higher oligomers.According to one aspect, the mixture of branched saturated hydrocarbonsis hydrogenated to the extent that the Bromine Index is below 1000 mgBr/100 g, as measured by ASTM D2710-0.

Base Oil

In one embodiment, the dimer portion of the hydrogenated oligomerproduct is separated from the remaining oligomer product, such as forexample by taking one or more distillation cuts of the hydrogenatedoligomer product.

In one embodiment, the saturated hydrocarbon base oil comprises greaterthan 90 wt % of the dimers, with the dimers having an average carbonnumber in the range of from 29 to 36, and the dimer portion having aweight average molecular weight in the range of from 422 to 510.Furthermore, according to embodiments herein, the dimers of thesaturated base oil can comprise an average branching index (B)) asdetermined by 1H NMR that is in the range of 22 to 26, and an averageparaffin branching proximity (BP) as determined by 13C NMR in a range offrom 18 to 26. The average paraffin branching proximity (BP) isdiscussed above, and is a measure of the content of recurring methylenegroups in the dimer portion. The branching index is a measure of theextent of branching, and can be determined according to the followingformula:

Branching index (BI)=(total content of methyl group hydrogens/totalcontent of hydrogens)*100

It has unexpectedly been discovered that, by controlling conditionsduring the base oil production process, including the oligomerizationand isomerization steps, to provide a dimer product with branchingcharacterized by the branching index and/or branching proximitydescribed herein, a base oil product can be achieved with improvedphysical properties that may be suitable for automotive engine oil andother applications. Further detail regarding the properties of the baseoil is described below.

To further clarify aspects of the present disclosure, it is noted thatPAO dimers made from C14-C18 alpha olefins (i.e., without exposure to anisomerization catalyst post-oligomerization) may have relatively highpour points which can prevent them from being used in engine oilformulations. Comparative Example A is a dimer of C14 and C16 alphaolefins that was hydrogenated without exposure to an isomerizing Zeolitecatalyst, and which has a BI of 22.51 and a branch proximity of 22.28;the pour point is −27° C. and a CCS at −35° C. of 2322 cP. Example 2according to aspects of this disclosure is a dimer of same ratio of C14to C16 alpha olefins as Comparative Example A, but which has beenfurther isomerized by exposure to a Zeolite catalyst beforehydrogenation, and which after hydrogenation exhibits a BI of 23.96 anda BP of 20.49; consequently, the pour point is −36° C. and a CCS at −35°C. of 1795 cP. This demonstrates that the isomerization process improvesthe pour point and CCS of the product.

In one embodiment, the isomerization of the oligomerized productproduces an oligomer that, after hydrogenation and distillation, has aparaffin branching proximity (BP) of greater than 18 and less than 26per 100 carbons and with branching index (BI) between 22 and 26 per 100carbons. For a base oil and/or dimer product having branching proximityand branching index within these ranges, sufficient long chain branchesremaining intact, while branching is also provided to a sufficientextent, resulting in a base oil with a viscosity index greater thanabout 125, with a pour point below −27° C., and CCS at −35° C. of lessthan 1800 cP.

An example of a resulting isomer structure can be seen in FIG. 6, with arepresentative process shown in FIG. 8. In this structure, a branchingindex (BI) is 24.2 per 100 carbons and a branching proximity (BP) is20.0 per 100 carbons. By contrast, FIG. 7 demonstrates a process andproduct by oligomerization and hydrogenation of C14 and C16 dimers,without a separate isomerization process, which results in less branchedstructures having a lower branching index of less than 19, and a higherbranching proximity of greater than 26. Similarly, referring to FIG. 4,a conventional 1-decene trimer has a lower branching index of 19.4 and alower branching proximity of 3, whereas, referring to FIG. 5, anoligomer produced by Fisher-Tropsch synthesis has a lower branchingindex of 19.4, and a higher branching proximity of 26.7. FIG. 9 furtherdemonstrates the results for a process that performs isomerization priorto hydrogenation (path A), versus a process that only performshydrogenation (path B). Accordingly, providing a dimer product with thebranching proximity (BP) and/or branching index (BI) as describedherein, such as via isomerization processes performedpost-oligomerization and prior to hydrogenation, can allow forproduction of a base oil having the improved physical properties.

In one embodiment, the dimer produced according to aspects of thisdisclosure, a C28 to 036 dimer, makes about a 4 cSt base oil and thephysical properties of the composition may have similar and/or improvedphysical properties as those that have yet only been achievable usingsolely 1-decene, or PAOs or those that incorporate significant amountsof 1-decene as a feedstock, such as PAOs derived from a mixedalpha-olefin feed of C10/C12, C8/C10/C12, C10/C12/C14 (i.e.,cross-oligomers of 010 and C12, and cross-oligomers of C8, C10 and C12).For example, aspects of the disclosure may provide a base oil comprisingthe dimer product with, e.g., about a 4 cSt KV100 base fluid, such as ina range of from about 3.7 to about 4.8 cSt, with excellent Noackvolatility, such as less than 14%, less than 1800 CCS at −35° C. andviscosity index (VI) greater than 125.

Furthermore, according to one aspect, the base oil compositioncomprising the dimer is substantially absent of any 1-decene. Forexample, embodiments of the base oil may comprise less than 5% by weightof 1-decene in either monomer, dimer, or trimer form, as well as higheroligomer forms, such as less than 3% by weight of 1-decene, and evenless than 1% by weight of 1-decene.

Previous attempts to utilize the long chain alpha olefins for a 4 cStbase fluid yielded hydrocarbon lubricants that were deficient in one ormore necessary physical parameters and they are included here forcomparison. Comparative Example A shows PAO made from C14 and C16 alphaolefins, where the oligomers are not isomerized, the product has a CCSat −35° C. of 2400 cP, that is too high to be desirable for engine oilsapplication due to rapid gelation characteristics. Changing the C14 andC16 content can help reduce the pour point, as shown by Reference A inthe below table (from U.S. Pat. No. 4,218,330). However, the extraaddition of C14 into the dimer is detrimental to the volatility as it isincreased past the desirable range of <14%. Comparative Example B ismade with C14 only dimers, and exhibits too low of a viscosity at 100°C., and too high a volatility, with its average carbon number of C28below the desired C29-36 range without isomerization of the oligomers.Comparative Example C contains C16 alpha olefins only and has C32average carbon length and an extremely low Noack volatility withoutisomerization of the oligomers. Instead, it has been discovered thatoligomers of alpha-olefins with an average carbon number greater thanabout C12 require isomerization after oligomerization, as disclosedherein, to bring the cold temperature properties to a desirable rangefor engine oils. Surprisingly, by controlling the oligomer chain length,branching index, and branching proximity through isomerization of theoligomers, as in Example 1 and 2, oligomers from long chain LAOs can beprepared that exhibit desirable engine oil properties.

TABLE 1 Olefin feed ratio effect on the properties on the C14-C16dimers. 100° C. Pour Noack viscosity, point, Volatility, Example FeedOlefins cSt VI ° C. % loss Comparative C14/C16 30/70 4.13 128 −27 12.6Example A Example 1 C4/C16 30/70 4.23 125 −39 12.9 Example 2 C14/C1630/70 4.24 128 −36 13.2 Reference A C14/C16 68/32 4.15 137 −26 >15Comparative C14 100 3.01 134 −30 16.1 Example B Comparative C16 100 4.30151 −15 6.4 Example C Example 3 C16 100 4.02 131 −33 13.9 Example 4 C16100 4.01 132 −30 13.3

For synthetic base oils such as PAO based on C8, C10, C12, or anycombination of C8 through C12 alpha olefins, the Branching Index (BI)has been found to correlate with improved lubricant properties forhydrocarbon base oils. Specifically, commercial PAO base oils based onC8 through C12 alpha olefins, as shown in Reference B (Commercial sampleof a 4 cSt PAO) in Table 2, require a Branching Index below about 22 toobtain desired properties. Oligomers from C8-C12 olefins with branchingindex greater than about 22 have excessive branching which constrainsthe lubricant properties, particularly with respect to viscosity index.Similarly, the Fischer-Tropsch process which produces gas to liquid(GTL) hydrocarbon lubricants with approximately 4 cSt at 100° C. amongother viscosity products, seen in Reference C and D, it is preferred tohave a branching index below 22 to achieve useful cold flow propertiesfor an engine oil, as seen in U.S. Pat. No. 7,018,525. In contrast, ashas been discovered herein, when using C14 or greater olefins, abranching index above 22 and a branching proximity of above 18 have beenfound to give superior lubricant properties, particularly with respectto VI, CCS at −35° c., and Noack volatility.

TABLE 2 Branching Index and average carbon number for samples of 4 cStGTL, PAO and this invention. Branching avg carbon Sample # Material idindex number Example 2 C14/C16 isom 23.96 30.8 Reference B GTL 19.7 27.8Reference C GTL 19 27.4 Reference D C8/C10/C12 PAO 21.8 32.4

TABLE 3 General comparison of 4 cSt C14-C16 dimer with PAO and GTL 4cStproducts. BI BP VI PP NV CCS @ −35 C. Example 2 24 20  128 <−33 <13<1800 PAO ≤22 ≤16 124-126 <−54 <14 <1500 GLT 4 <20 >26 >140 −27 14 >1800

According to one embodiment, the saturated hydrocarbon base oilcomprising the dimer product exhibits improved properties, such asvolatility and cold temperatures properties suitable for use inautomotive engine oil formulations. In one embodiment, the saturatedhydrocarbon base oil comprising the dimer product exhibits a NoackVolatility as measured by ASTM D5800 that is less than 14%. In yetanother embodiment, the saturated hydrocarbon base oil comprising thedimer product exhibits a Noack Volatility as measured by ASTM D5800 thatis less than 13%. In yet another embodiment, the saturated hydrocarbonbase oil comprising the dimer product exhibits a Noack Volatility asmeasured by ASTM D5800 that is less than 12%. In yet another embodiment,the saturated hydrocarbon base oil comprising the dimer product exhibitsa Noack Volatility as measured by ASTM D5800 that is less than 11%. Inyet another embodiment, the saturated hydrocarbon base oil comprisingthe dimer product exhibits a Noack Volatility as measured by ASTM D5800that is less than 10%. In yet another embodiment, the saturatedhydrocarbon base oil comprising the dimer product exhibits a NoackVolatility as measured by ASTM D5800 that is less than 9%. In yetanother embodiment, the saturated hydrocarbon base oil comprising thedimer product exhibits a Noack Volatility as measured by ASTM D5800 thatis less than 8%. In yet another embodiment, the saturated hydrocarbonbase oil comprising the dimer product exhibits a Noack Volatility asmeasured by ASTM D5800 that is less than 7%. Generally, the NoackVolatility will be at least 6%.

According to yet another embodiment, the saturated hydrocarbon base oilcomprising the dimer product exhibits a Pour Point as measured by ASTMD97-17 of less than −27° C. According to yet another embodiment, thesaturated hydrocarbon base oil comprising the dimer product exhibits aPour Point as measured by ASTM D97-17 of less than −30° C. According toyet another embodiment, the saturated hydrocarbon base oil comprisingthe dimer product exhibits a Pour Point as measured by ASTM D97-17 ofless than −33° C. According to yet another embodiment, the saturatedhydrocarbon base oil comprising the dimer product exhibits a Pour Pointas measured by ASTM D97-17a of less than −36° C. According to yetanother embodiment, the saturated hydrocarbon base oil comprising thedimer product exhibits a Pour Point as measured by ASTM D97-17a of lessthan −39° C. According to yet another embodiment, the saturatedhydrocarbon base oil comprising the dimer product exhibits a Pour Pointas measured by ASTM D97-17a of less than −42° C.

According to one embodiment, the saturated hydrocarbon base oilcomprising the dimer product exhibits a Cold Crank Simulated (CCS)dynamic viscosity as measured by ASTM D5293 at −35° C. of 1800 cP orless. According to yet another embodiment, the saturated hydrocarbonbase oil comprising the dimer product exhibits a Cold Crank Simulated(CCS) dynamic viscosity as measured by ASTM D5293-15 at −35° C. of 1700cP or less. According to yet another embodiment, the saturatedhydrocarbon base oil comprising the dimer product exhibits a Cold CrankSimulated (CCS) dynamic viscosity as measured by ASTM D5293-15 at −35°C. of 1600 cP or less. According to yet another embodiment, thesaturated hydrocarbon base oil comprising the dimer product exhibits aCold Crank Simulated (CCS) dynamic viscosity as measured by ASTMD5293-15 at −35° C. of 1500 cP or less. According to yet anotherembodiment, the saturated hydrocarbon base oil comprising the dimerproduct exhibits a Cold Crank Simulated (CCS) dynamic viscosity asmeasured by ASTM D5293-15 at −35° C. of 1400 cP or less. According toyet another embodiment, the saturated hydrocarbon base oil comprisingthe dimer product exhibits a Cold Crank Simulated (CCS) dynamicviscosity as measured by ASTM D5293-15 at −35° C. of 1300 cP or less.According to yet another embodiment, the saturated hydrocarbon base oilcomprising the dimer product exhibits a Cold Crank Simulated (CCS)dynamic viscosity as measured by ASTM D5293-15 at −35° C. of 1200 cP orless According to yet another embodiment, the saturated hydrocarbon baseoil comprising the dimer product exhibits a Cold Crank Simulated (CCS)dynamic viscosity as measured by ASTM D5293-15 at −35° C. of less than1100 cP.

Furthermore, in one embodiment, the saturated hydrocarbon base oilcomprising the dimer product exhibits a KV(100) as measured by ASTMD445-17a that is in the range of from 3.7 cSt to 4.8 cSt. In anotherembodiment, the saturated hydrocarbon base oil comprising of the dimerproduct exhibits a KV100 as measured by ASTM D445-17a is in the range offrom 3.8 cSt to 4.5 cSt.

In another embodiment, the saturated hydrocarbon base oil comprising thedimer product exhibits a viscosity index as measured by ASTM D2270 of125 or greater. In yet another embodiment, the saturated hydrocarbonbase oil comprising the dimer product exhibits a viscosity index asmeasured by ASTM D2270 of 130 or greater. In yet another embodiment, thesaturated hydrocarbon base oil comprising the dimer product exhibits aviscosity index as measured by ASTM D2270 of 135 or greater. In yetanother embodiment, the saturated hydrocarbon base oil comprising thedimer product exhibits a viscosity index as measured by ASTM D2270 of140 or greater. In yet another embodiment, the saturated hydrocarbonbase oil comprising the dimer product exhibits a viscosity index asmeasured by ASTM D2270 of 150 or greater.

In yet another embodiment, the saturated hydrocarbon base oil has aNoack Volatility that is related to the KV100 by the following equation:

Noack volatility<−16.583(KV100){circumflex over( )}2+125.36(KV100)+223.8

In yet another embodiment, the CCS at −35 is related to the KV 100 bythe following equation:

CCS viscosity at −35° C.<−1333.3(KV100){circumflex over( )}2+11933(KV100)−24900.

EXAMPLES

The following examples are meant to illustrate embodiments of thepresent disclosure, and it will be recognized by one of ordinary skillin the art in possession that numerous modifications and variations arepossible. Therefore, it is to be understood that embodiments of theinvention may be practiced otherwise than as specifically describedherein.

Example 1

An olefin mixture of 30% 1-tetradecene and 70% 1-hexadecene with lessthan 8% branched and internal olefins was obtained, and the mixture wasoligomerized under BF₃ pressure with a co-catalyst comprising a shortchain alcohol and ester. Semi continuous addition of olefins andco-catalyst was used. The monomer was then distilled off and the bottomswere isomerized using a zeolite on alumina catalyst at 250° C. for 8hours in a batch reactor. The isomerized oligomers were thenhydrogenated to a Bromine Index of less than 1000 mg Br/100 g. Thehydrogenated dimers were then distilled away from the trimer and heavieroligomers and had an average branching proximity of 22.3.

Example 2

Oligomerization reaction and feeds were carried out in accordance withExample 1. The remaining monomer was distilled off and the resultingoligomers were exposed to a zeolite on alumina catalyst at 270° C. for 8hours in a batch reactor.

Example 3

A 1-hexadecene olefin feed with less than 8% branched and internalolefins was obtained. The 1-hexadecene feed was oligomerized under BF₃pressure with a co-catalyst comprising of a short chain alcohol andester. Semi continuous addition of olefins and co-catalyst was used. Theunreacted monomer was then distilled off and the bottoms were isomerizedusing a zeolite on alumina catalyst at 290° C. for 4 hours in a batchreactor. The isomerized oligomers were then hydrogenated to a BromineIndex of less than 1000 mg Br/100 g. The Hydrogenated dimers were thendistilled away from the trimer and heavier oligomers.

Example 4

Oligomerization feed and reaction was carried out in accordance withExample 3. The remaining monomer was distilled off and the resultingoligomers were exposed to a zeolite on alumina catalyst at 270° C. for 4hours.

Definitions

Olefin

The term “Olefin” as used herein refers a hydrocarbon containing atleast one carbon-carbon double bond. For example, according to aspectsof the disclosure herein, an olefin may comprise a hydrocarbon chainlength of from C14 to C18, and may have a double bond at an end (primaryposition) of the hydrocarbon chain (alpha-olefin) or at an internalposition (internal-olefin). In one embodiment, the olefin is amono-olefin, meaning that the olefin contains only a single double-bondgroup.

Alpha Olefins

The term “Alpha Olefin” as used herein refers an olefin that has acarbon-carbon double bond at an end of the olefin hydrocarbon chain(terminal position). For example, according to aspects of the disclosureherein, alpha olefins may comprise a hydrocarbon chain size of from C14to C18, such as compounds having a chemical formula where the olefin hasno more carbons than the specified carbon number of C14 to C18, e.g.,C14H28, C16H32 and C18H36. In one embodiment, the alpha olefin is amono-alpha-olefin, meaning that the alpha olefin contains only a singledouble-bond group.

Linear Alpha Olefin (LAO)

The term “Linear Alpha Olefin” as used herein refers an olefin that islinear (i.e., unbranched), and has a double bond at an end of the olefinhydrocarbon chain (terminal position). For example, according to aspectsof the disclosure herein, alpha olefins may comprise a hydrocarbon chainlength of from C14 to C18, such as compounds having a chemical formulawhere the olefin has no more carbons than the specified carbon number ofC14 to C18, e.g., C14H28, C16H32 and C18H36. In one embodiment, thelinear alpha olefin is a mono-alpha-olefin, meaning that the alphaolefin contains only a single double-bond group.

Internal Olefins

The term “Internal Olefin” as used herein refers an olefin that has aninternal carbon-carbon double bond that is interior to the terminal endof the olefin hydrocarbon chain (e.g., at a position other than thealpha-position), and does not contain a carbon-carbon double bond at theterminal position. For example, according to aspects of the disclosureherein, internal olefins may comprise a hydrocarbon chain size of fromC14 to C18, such as compounds having a chemical formula where the olefinhas no more carbons than the specified carbon number of C14 to C18, e.g.C14H28, C16H32 and C18H36. In one embodiment, the internal olefin is amono-internal-olefin, meaning that the internal olefin contains only asingle double-bond group.

Linear Internal Olefins

The term “Linear Internal Olefin” as used herein refers an olefin thatis linear (i.e., unbranched), and that has a carbon-carbon double bondthat is interior to the terminal end of the olefin hydrocarbon chain(e.g., at a position other than the alpha-position), and does notcontain a carbon-carbon double bond at the terminal position. Forexample, according to aspects of the disclosure herein, linear internalolefins may comprise a hydrocarbon chain length of from C14 to C18, suchas compounds having a chemical formula where the olefin has no morecarbons than the specified carbon number of C14 to C18, e.g. C14H28,C16H32 and C18H36. In one embodiment, the linear internal olefin is amono-internal-olefin, meaning that the linear internal olefin containsonly a single double-bond group.

Linear Mono-Olefins

Mixture of olefins or alkenes distinguished from other olefins with asimilar molecular formula by linearity of the hydrocarbon chain lengthand a distribution of double bond positions in the molecule, from alphato internal position. For example, according to aspects of thedisclosure herein, linear mono-olefins may comprise a hydrocarbon chainlength of from C14 to C18 with a chemical formula C14H28, C16H32,C18H36.

Isomerized Olefin

The term “Isomerized Olefin” is used herein to refer to an olefin feedand/or mixture that has been subjected to an isomerization process, suchthat an average double-bond position in the olefin and/or olefins feedhas been shifted from a position close to or at the terminal doubleposition (alpha position), to a distribution of cis/trans double bondpositions more interior along the chain length. For example, in oneembodiment, isomerized olefins can be formed by isomerization of linearalpha olefins (LAO), which have their double bond at the terminal end ofthe hydrocarbon chain, to linear internal olefins having an averagedouble bond position more interior along the chain.

Branched Alpha-Olefins

The term “Branched Alpha-Olefin” is used herein to refer to an olefinthat has alkyl (such as methyl or ethyl) branch groups along thehydrocarbon chain length of the olefin, and has a double bond at an endof the olefin hydrocarbon chain (primary position). For example,according to aspects of the disclosure herein, branched alpha olefinsmay comprise C14 to C18 olefins. In one embodiment, the branched alphaolefin is a mono-alpha-olefin, meaning that the branched alpha olefincontains only a single double-bond group.

Branched Internal Olefins

The term “Branched Internal-Olefin” is used herein to refer to an olefinthat has alkyl (such as methyl or ethyl, or even longer) branch groupsalong the hydrocarbon chain length of the olefin, and has a double bondthat is interior to the terminal end of the olefin hydrocarbon chain(e.g., at a position other than the alpha-position), and does notcontain a carbon-carbon double bond at the terminal position. Forexample, according to aspects of the disclosure herein, branchedinternal olefins may comprise C14 to C18 olefins. In one embodiment, thebranched internal olefin is a mono-alpha-olefin, meaning that thebranched alpha olefin contains only a single double-bond group.

Dimer

The term “Dimer” as used herein refers to molecules formed by thecombination of two monomers via a chemical process, where in monomersmay be the same or different type of monomer unit. The dimer may beformed by chemical reaction and/or other type of bonding between themonomers. In one embodiment, a dimer is the product of oligomerizationbetween two olefin monomers.

Oligomer

The term “oligomer” as used herein refers to a molecule having 2-100monomeric units, and encompasses dimers, trimers, tetramers, pentamers,and hexamers. An oligomer may comprise one type of monomer unit or morethan one type of monomer unit, for example, two types of monomer units,or three types of monomer units. “Oligomerization” as used herein refersto the formation of a molecule having 2-100 monomeric units from one ormore monomers, and encompasses dimerization, trimerization, etc. of onetype or different types of monomer, and also encompasses the formationof adducts and/or complexes between the same or more than one type ofmonomer.

Dimer Total Carbon Number

The term “Dimer Total Carbon Number” is used herein to refer to a totalnumber of carbons in the dimer. Accordingly, a “C29-C36” dimer asreferred to herein is a dimer have a total number of carbon atoms in arange of from 29 to 36.

Terpenes

The term “Terpenes” as used herein refers to compounds having multiplesof units of isoprene, which has the molecular formula C₅H₈. The basicmolecular formula of terpenes are multiples of that, (C₅H₈)_(n) where nis the number of linked isoprene units, and terpenes can be derivedbiosynthetically from such units of isoprene. Monoterpenes consist oftwo isoprene units and have the molecular formula C₁₀H₁₆. Sesquiterpenesconsist of three isoprene units.

Renewable

The term “Renewable” as used herein means any biologically derivedcomposition, including fatty alcohols, olefins, or oligomers. Suchcompositions may be made, for nonlimiting example, from biologicalorganisms designed to manufacture specific oils, as discussed in WO2012/141784, but do not include petroleum distilled or processed oilssuch as, for non-limiting example, mineral oils. A suitable method toassess materials derived from renewable resources is through “StandardTest Methods for Determining the Biobased Content of Solid, Liquid, andGaseous Samples Using Radiocarbon Analysis” (ASTM D6866-12 or ASTMD6866-11). Counts from ¹⁴C in a sample can be compared directly orthrough secondary standards to SRM 4990C. A measurement of 0% ¹⁴Crelative to the appropriate standard indicates carbon originatingentirely from fossils (e.g., petroleum based). A measurement of 100% ¹⁴Cindicates carbon originating entirely from modern sources (See, e.g., WO2012/141784, incorporated herein by reference).

Base Oil

The term “Base Oil” as used herein refers an oil used to manufactureproducts including dielectric fluids, hydraulic fluids, compressorfluids, engine oils, lubricating greases, and metal processing fluids.

Viscosity Index

The term “Viscosity index” as used herein refers to viscosity index asmeasured according to “Standard Practice for Calculating Viscosity IndexFrom Kinematic Viscosity at 40 and 100° C.” (ASTM D2270) published byASTM International, which is incorporated herein by reference in itsentirety.

Kinematic Viscosity

The term “Kinematic Viscosity” as used herein refers to viscosities at40° C. and at 100° C. measured according to “Standard Test Method forKinematic Viscosity of Transparent and Opaque Liquids (and Calculationof Dynamic Viscosity)” (ASTM D445-17a) published by ASTM International,which is incorporated herein by reference in its entirety.

Cold-Cranking Simulator Viscosity

The term “Cold-Cranking Simulator Viscosity” (abbreviated CCS) refers tocold cranking simulator viscosity as measured according to “StandardTest Method for Apparent Viscosity of Engine Oils Between −5 and −35° C.Using the Cold-Cranking Simulator” (ASTM D5293) published by ASTMInternational, which is incorporated herein by reference in itsentirety.

Pour Point

The term “Pour Point” refers to temperature at which a lubricant becomessemi solid and at least partially loses its flow characteristics, and ismeasured according to “Standard Test Method for Pour Point of PetroleumProducts” (ASTM D97) published by ASTM International, which isincorporated herein by reference in its entirety.

Noack Volatility

The term “Noack Volatility” is used herein to a measure of evaporativeweight loss as carried out according to “Standard Test Method forEvaporation Loss of Lubricating Oils by the Noack Method” (ASTM D5800),or “Standard Test Method for Evaporation Loss of Lubricating Oils byThermogravimetric Analyzer (TGA) Noack Method” (ASTM D6375, TGA-Noackmethod), each published by ASTM International, and each of which isincorporated herein by reference in its entirety.

Bromine Index

The term “Bromine Index” is used herein to refer to a test fordetermining the degree of unsaturation of a product, such as ahydrogenated oligomer and/or dimer product, and can be determined inaccordance with ASTM D2710-09, which is incorporated by reference hereinin its entirety.

Branching Index (BI)

The term “Branching Index” is referred to herein as a measure of thepercentage of methyl protons divided by the total number of protons(non-benzylic) in a sample, such as a sample comprising a dimer oroligomer. According to one embodiment, the Branching Index can becalculated using 1H NMR, by determining the percent of the non-benzylicmethyl hydrogen content in the range of 0.5 to 1.05 ppm, per the totalnon-benzylic aliphatic hydrogen content in the range of 0.5 to 2.1 ppm.The formula for calculating the Branching Index is as follows:

Branching Index (BI)=(total content of methyl group hydrogens/totalcontent of hydrogens)*100.

Measurement of the Branching Index is further described in U.S. Pat.Nos. 6,090,989 and 7,018,525, both of which are hereby incorporated byreference herein in their entireties.

Branch Proximity (BP)

The term “Branching Proximity” is used herein is used to refer to the %equivalent recurring methylene carbons, which are four or more removedfrom a carbon end group or branching carbon group (e.g., the epsiloncarbons as shown in FIG. 3). In one embodiment, the Branching Proximitycan be evaluated using 13C NMR, by measuring a peak corresponding to therecurring methylene carbons (e.g., at about 29.8 ppm), and determiningthe content as a percent of all carbon atoms measured in the 13C NMRspectrum. According to one aspect, the Branching Proximity may bedetermined according to the following formula:

Branching Proximity (BP)=(number of ε carbon groups/total number ofcarbon groups)*100,

where an ε carbon group is defined as a carbon group that is separatedfrom any terminal carbon atom groups or branching carbon groups by atleast 4 carbon groups. Further description of the measurement of theBranching Proximity is described in U.S. Pat. No. 6,090,989, and furtherdescription of epsilon carbons is providing in U.S. 2008/0171675, bothof which are hereby incorporated by reference herein in theirentireties.

PIOs

PIOs refer to dimer, trimer or larger oligomer that is the product of anoligomerization which uses internal olefins as the feedstock.

PAOs

PAOs refer to dimer, trimer or larger oligomer that is the product of anoligomerization which uses alpha olefins as the feedstock.

Aspects of the invention may further be described with respect to thefollowing embodiments:

Embodiment 1: A process for the preparation of a saturated hydrocarbonbase oil, comprising:

-   -   forming an oligomerization reaction mixture comprising an        oligomerization catalyst system and an olefin monomer feed        mixture, wherein the olefin monomer feed mixture has an average        carbon number in the range of 14 to 18;    -   oligomerizing the olefin monomer feed mixture in the reaction        mixture to produce an oligomer product comprising dimers,        trimers, and higher oligomers,    -   isomerizing at least the dimer portion of the oligomer product        in the presence of an acid catalyst to form a mixture of        branched hydrocarbons;    -   hydrogenating the isomerized branched hydrocarbons, to a Bromine        Index below 1000 mg Br₂/100 g as determined in accordance with        ASTM D2710-09; and    -   separating the dimer portion of the hydrogenated oligomer        product, whereby a saturated hydrocarbon base oil is obtained        comprising greater than 90 wt % dimers having an average carbon        number in the range of from 29 to 36, the dimer portion having a        weight average molecular weight in the range of from 422 to 510,    -   wherein the dimers of the oligomer product, in a case where the        dimers are hydrogenated to a Bromine Index below 1000 mg Br₂/100        g as determined in accordance with ASTM D2710-09, without        subsequent isomerizing, have an average paraffin branching        proximity (BP) as determined by 13C NMR of 20 or greater, and    -   wherein the isomerized and hydrogenated dimers of the saturated        hydrocarbon base oil have an average branching index (BI) as        determined by 1H NMR that is in the range of from 22 to 26, and        an average paraffin branching proximity (BP) as determined by        13C NMR in a range of from 18 to 26,    -   wherein the branching index (BI) is determined as follows:

branching index (BI)=(total content of methyl group hydrogens/totalcontent of hydrogens)*100, and

-   -   wherein the paraffin branching proximity (BP) is determined as        follows:

paraffin branching proximity (BP)=(number of ε carbon groups/totalnumber of carbon groups)*100,

-   -   where an ε carbon group is defined as a carbon group that is        separated from any terminal carbon atom groups or branching        carbon groups by at least 4 carbon groups.

Embodiment 2: The process according to embodiment 1, wherein theoligomerization conditions during oligomerization result in dimers ofthe oligomer product that, in a case where the dimers are hydrogenatedto a Bromine Index below 1000 mg Br₂/100 g as determined in accordancewith ASTM D2710-09, without subsequent isomerizing, have an average aparaffin branching proximity (BP) of 22 or greater.

Embodiment 3: The process according to any preceding embodiment,comprising performing the isomerization after oligomerization of theolefin feed mixture had been performed.

Embodiment 4: The process according to any preceding embodiment, whereinat least a portion of the isomerization is performed simultaneously witholigomerization.

Embodiment 5: The process according to any preceding embodiment, whereinthe olefin monomer feed mixture comprises a first feedstock comprisingC14 to C18 alpha olefin monomers selected from the group consisting oftetradecene, pentadecene, hexadecene, heptadecene and octadecene.

Embodiment 6: The process according to any preceding embodiment, furthercomprising preparing an olefin monomer feed mixture comprising C14 toC18 alpha olefin monomers by dehydration of C14 to C18 primary alcoholsselected from the group consisting of 1-tetradecanol, 1-pentadecanol,1-hexadecanol, 1-heptadecanol and 1-octadecanol.

Embodiment 7: The process according to any preceding embodiment, whereinthe olefin monomer feed mixture comprises olefin monomers selected fromthe group consisting of unsaturated, linear alpha-olefins; unsaturated,normal internal-olefins; branched alpha-olefins; branchedinternal-olefins; and combinations thereof.

Embodiment 8: The process according to any preceding embodiment, wherethe olefin monomer feed mixture comprises a mixture of linearalpha-olefins and/or linear internal-olefins.

Embodiment 9: The process according to any preceding embodiment, whereinthe olefin monomer feed mixture comprises olefin monomers selected fromthe group consisting of unsaturated olefin comprises, linearalpha-olefins; linear internal-olefins; branched alpha-olefins; branchedinternal-olefins; and combinations thereof.

Embodiment 10: The process according to any preceding embodiment,wherein the olefin monomer feed mixture comprises a first feedstockcomprises less than 36% by weight of branched olefin monomers.

Embodiment 11: The process of any preceding embodiment, wherein theolefin monomer feed mixture comprises a first feedstock comprising lessthan 20% by weight of branched olefin monomers.

Embodiment 12: The process of any preceding embodiment, wherein theolefin monomer feedstock comprises a first feedstock comprising lessthan 10% by weight of branched olefin monomers.

Embodiment 13: The process of any preceding embodiment, wherein theolefin monomer feedstock comprises a first feedstock comprising lessthan 5% by weight of branched olefin monomers.

Embodiment 14: The process of any preceding embodiment, wherein anamount of decene in any of first and/or second feedstocks of the olefinmonomer feedstock is less than 20% by weight.

Embodiment 15: The process of any preceding embodiment, wherein anamount of decene in any of first and/or second feedstocks of the olefinmonomer feedstock is less than 10% by weight.

Embodiment 16: The process of any preceding embodiment, wherein anamount of decene in any of first and/or second feedstocks of the olefinmonomer feedstock is less than 5% by weight.

Embodiment 17: The process of any preceding embodiment, furthercomprising oligomerizing the olefin monomer feed under conditions to atleast partially isomerize the dimers, trimers, and higher oligomers.

Embodiment 18: The process of any preceding embodiment, wherein theunreacted monomer is distilled from the unsaturated oligomers andrecycled in a subsequent oligomerization reaction.

Embodiment 19: The process of any preceding embodiment, whereinisomerizing of the oligomer product is performed in the absence ofhydrogen.

Embodiment 20: The process according to any preceding embodiment,wherein an amount of cracked byproducts generated during isomerizing ofthe oligomer product is less than 10%.

Embodiment 21: The process according to any preceding embodiment,wherein an amount of cracked byproducts generated during isomerizing ofthe oligomer product is less than 5%.

Embodiment 22: The process according to any preceding embodiment,wherein an amount of cracked byproducts generated during isomerizing ofthe oligomer product is less than 1%.

Embodiment 23: The process according to any preceding embodiment,wherein isomerizing of the oligomer product is performed at atemperature in the range of from 125° C. to 300° C., and a pressure inthe range of from 1 PSI to 100 PSI of inert gas, in the presence of anacid catalyst selected from the group consisting of solid metals ormetal oxides or their mixture of Group IVB, VB, VIB and Group metaloxides or mixed oxides of Group IIA to VA; mixed metal oxides comprisingWO_(x)/ZrO₂ type catalyst; solid natural or synthetic zeolites; andlayered material, crystalline or amorphous material of silica, alumina,silicoaluminate, aluminophosphate, aluminum silicophosphate.

Embodiment 24: The process according to any preceding embodiment,wherein the dimer portion of the isomerized oligomer product isseparated by distillation from the isomerized oligomer product.

Embodiment 25: The process of any preceding embodiment where theoligomerization reaction is carried out at a temperature range from10-110° C.

Embodiment 26: The process of any preceding embodiment, wherein theoligomerization catalyst is selected from the group consisting ofzeolites, Friedel-Crafts catalysts, Bronsted acids, Lewis acids, acidicresins, acidic solid oxides, acidic silico aluminophosphates, Group IVBmetal oxides, Group VB metal oxides, Group VIB metal oxides, hydroxideor free metal forms of Group VIII metals, and any combination thereof.

Embodiment 27: The process of any preceding embodiment, wherein theoligomerization reaction catalyst is BF₃, and the promoter is an alcoholand/or an ester.

Embodiment 28: The process of any preceding embodiment, wherein theoligomerization is carried out in at least one continuously stirredreactor under oligomerization conditions with an average residence timeof 60 to 400 minutes.

Embodiment 29: The process of any preceding embodiment, wherein theoligomerization is carried out in at least one continuously stirredreactor under oligomerization conditions with an average residence timeof 90 to 300 minutes.

Embodiment 30: The process of any preceding embodiment, wherein theoligomerization is carried out in at least one continuously stirredreactor under oligomerization conditions with an average residence timeof 120 to 240 minutes.

Embodiment 31: The process of any preceding embodiment, wherein the acidcatalyst used for isomerizing the unsaturated polyolefin is a zeolitehaving a Constraint Index of about 2 to about 12.

Embodiment 32: The process of any preceding embodiment, wherein the acidcatalyst used for isomerizing the unsaturated polyolefin is a zeolitecontaining one or more Group VI B to VIII B metal elements.

Embodiment 33: The process of any preceding embodiment, wherein the pourpoint of the isomerization product is at least −9 less than that of theoligomer product prior to isomerization.

Embodiment 34: The process according to any preceding embodiment,wherein the pour point of the isomerization product is at least −15° C.less than that of the oligomer product prior to isomerization.

Embodiment 35: The process according to any preceding embodiment,wherein the pour point of the isomerization product is at least −21° C.less than that of the oligomerization product prior to isomerization.

Embodiment 36: The process according to any preceding embodiment,wherein the dirtier product of the saturated hydrocarbon base oil has <5wt % naphthalenes after isomerization and hydrogenation.

Embodiment 37: The process according to any preceding embodiment,wherein the dimer product of the saturated hydrocarbon base oil has <2.5wt % naphthalenes after isomerization and hydrogenation.

Embodiment 38: The process of any preceding embodiment, wherein thedimer product of the saturated hydrocarbon base oil has <1 wt %naphthalenes after isomerization and hydrogenation.

Embodiment 39: The process of any preceding embodiment, wherein apercent yield of isomerized dinners produced in the isomerization is >90wt. %.

Embodiment 40: The process according to any preceding embodiment,wherein a percent yield of isomerized dimers produced in theisomerization >95 wt, %.

Embodiment 41: The process according to any preceding embodiment,wherein a percent yield of isomerized dimers produced in theisomerization >97.5 wt. %.

Embodiment 42: The process according to any preceding embodiment,wherein a percent yield of isomerized dimers produced in theisomerization is >99 wt, %.

Embodiment 43: The process according to any preceding embodiment,wherein the base oil has a kinematic viscosity of measured at 100° C. byASTM D445 of 3.7 cSt to 4.8 cSt.

Embodiment 44: The process according to any preceding embodiment,wherein the base oil has a kinematic viscosity of measured at 100° C. byASTM D445 of 3.8 cSt to 4.5 cSt.

Embodiment 45: The process according to any preceding embodiment,wherein the saturated base oil has a Viscosity Index 125 or greater.

Embodiment 46: The process according to any preceding embodiment,wherein the saturated base oil has a Viscosity Index 130 or greater.

Embodiment 47: The process according to any preceding embodiment,wherein the base oil has a Viscosity Index 135 or greater.

Embodiment 48: The process according to any preceding embodiment,wherein the base oil has a Viscosity Index 140 or greater.

Embodiment 49: The process according to any preceding embodiment,wherein the base oil has a Viscosity Index of 150 or greater.

Embodiment 50: The process according to any preceding embodiment,wherein the base oil has a CCS at −35° C. less than 1800 cP.

Embodiment 51: The process according to any preceding embodiment,wherein the base oil has a CCS at −35° C. less than 1700 cP.

Embodiment 52: The process according to any preceding embodiment,wherein the base oil has a CCS at −35° C. less than 1600 cP.

Embodiment 53: The process according to any preceding embodiment,wherein the base oil has a CCS at −35° C. less than 1500 cP.

Embodiment 54: The process according to any preceding embodiment,wherein the base oil has a CCS at −35° C. less than 1400 cP.

Embodiment 55: The process according to any preceding embodiment,wherein the base oil has a CCS at −35° C. less than 1300 cP.

Embodiment 56: The process according to any preceding embodiment,wherein the base oil has a CCS at −35° C. less than 1200 cP.

Embodiment 57: The process according to any preceding embodiment,wherein the base oil has a CCS at −35° C. less than 1100 cP.

Embodiment 58: The process according to any preceding embodiment,wherein the base oil has a Noack volatility less than 14%.

Embodiment 59: The process according to any preceding embodiment,wherein the base oil can be characterized by a Noack volatility of lessthan 13%.

Embodiment 60: The process according to any preceding embodiment,wherein the base oil can be characterized by Noack volatility of lessthan 12%.

Embodiment 61: The process according to any preceding embodiment,wherein the base oil can be characterized by Noack volatility of lessthan 11%.

Embodiment 62: The process according to any preceding embodiment,wherein the base oil can be characterized by Noack volatility of lessthan 10%.

Embodiment 63: The process according to any preceding embodiment,wherein the base oil can be characterized by Noack volatility of lessthan 9%.

Embodiment 64: The process according to any preceding embodiment,wherein the base oil can be characterized by Noack volatility of lessthan 8%.

Embodiment 65: The process according to any preceding embodiment,wherein the base oil can be characterized by Noack volatility of lessthan 7%.

Embodiment 66: The process according to any preceding embodiment,wherein the base oil can be characterized by Noack volatility of lessthan 6%.

Embodiment 67: The process according to any preceding embodiment,wherein the base oil can be characterized by pour point of less than−27° C.

Embodiment 68: The process according to any preceding embodiment,wherein the base oil can be characterized by pour point of less than−30° C.

Embodiment 69: The process according to any preceding embodiment,wherein the base oil can be characterized by pour point of less than−33° C.

Embodiment 70: The process according to any preceding embodiment,wherein the base oil can be characterized by pour point of less than−36° C.

Embodiment 71: The process according to any preceding embodiment,wherein the base oil can be characterized by pour point of less than−39° C.

Embodiment 72: The process according to any preceding embodiment,wherein the base oil can be characterized by pour point of less than−42° C.

Embodiment 73: The process according to any preceding claim, where acatalyst provided during isomerization is other than a catalyst providedduring oligomerization.

What is claimed:
 1. A process for the preparation of a saturatedhydrocarbon base oil, comprising: forming an oligomerization reactionmixture comprising an oligomerization catalyst system and an olefinmonomer feed mixture, wherein the olefin monomer feed mixture has anaverage carbon number in the range of 14 to 18; oligomerizing the olefinmonomer feed mixture in the reaction mixture to produce an oligomerproduct comprising dimers, trimers, and higher oligomers, isomerizing atleast the dimer portion of the oligomer product in the presence of anacid catalyst to form a mixture of branched hydrocarbons; hydrogenatingthe isomerized branched hydrocarbons, to a Bromine Index below 1000 mgBr₂/100 g as determined in accordance with ASTM D2710-09; and separatingthe dimer portion of the hydrogenated oligomer product, whereby asaturated hydrocarbon base oil is obtained comprising greater than 90 wt% dimers having an average carbon number in the range of from 29 to 36,the dimer portion having a weight average molecular weight in the rangeof from 422 to 510, wherein the dimers of the oligomer product, in acase where the dimers are hydrogenated to a Bromine Index below 1000 mgBr₂/100 g as determined in accordance with ASTM D2710-09, withoutsubsequent isomerizing, have an average paraffin branching proximity(BP) as determined by 13C NMR of 20 or greater, and wherein theisomerized and hydrogenated dimers of the saturated hydrocarbon base oilhave an average branching index (BI) as determined by 1H NMR that is inthe range of from 22 to 26, and an average paraffin branching proximity(BP) as determined by 13C NMR in a range of from 18 to 26, wherein thebranching index (BI) is determined as follows:branching index (BI)=(total content of methyl group hydrogens/totalcontent of hydrogens)*100, and wherein the paraffin branching proximity(BP) is determined as follows:paraffin branching proximity (BP)=(number of ε carbon groups/totalnumber of carbon groups)*100, where an ε carbon group is defined as acarbon group that is separated from any terminal carbon atom groups orbranching carbon groups by at least 4 carbon groups
 2. The processaccording to claim 1, wherein the oligomerization conditions duringoligomerization result in dimers of the oligomer product that, in a casewhere the dimers are hydrogenated to a Bromine Index below 1000 mgBr₂/100 g as determined in accordance with ASTM D2710-09, withoutsubsequent isomerizing, have an average a paraffin branching proximity(BP) of 22 or greater.
 3. The process according to any preceding claim,comprising performing the isomerization after oligomerization of theolefin feed mixture had been performed.
 4. The process according to anypreceding claim, wherein at least a portion of the isomerization isperformed simultaneously with oligomerization.
 5. The process accordingto any preceding claim, wherein the olefin monomer feed mixturecomprises a first feedstock comprising C14 to C18 alpha olefin monomersselected from the group consisting of tetradecene, pentadecene,hexadecene, heptadecene and octadecene.
 6. The process according to anypreceding claim, further comprising preparing an olefin monomer feedmixture comprising C14 to C18 alpha olefin monomers by dehydration ofC14 to C18 primary alcohols selected from the group consisting of1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol and1-octadecanol.
 7. The process according to any preceding claim, whereinthe olefin monomer feed mixture comprises olefin monomers selected fromthe group consisting of unsaturated, linear alpha-olefins; unsaturated,normal internal-olefins; branched alpha-olefins; branchedinternal-olefins; and combinations thereof.
 8. The process according toany preceding claim, where the olefin monomer feed mixture comprises amixture of linear alpha-olefins and/or linear internal-olefins.
 9. Theprocess according to any preceding claim, wherein the olefin monomerfeed mixture comprises olefin monomers selected from the groupconsisting of unsaturated olefin comprises, linear alpha-olefins; linearinternal-olefins; branched alpha-olefins; branched internal-olefins; andcombinations thereof.
 10. The process according to any preceding claim,wherein the olefin monomer feed mixture comprises a first feedstockcomprising less than 36% by weight of branched olefin monomers.
 11. Theprocess of any preceding claim, wherein the olefin monomer feed mixturecomprises a first feedstock comprising less than 20% by weight ofbranched olefin monomers.
 12. The process of any preceding claim,wherein the olefin monomer feedstock comprises a first feedstockcomprising less than 10% by weight of branched olefin monomers.
 13. Theprocess of any preceding claim, wherein the olefin monomer feedstockcomprises a first feedstock comprising less than 5% by weight ofbranched olefin monomers.
 14. The process of any preceding claim,wherein an amount of decene in any of first and/or second feedstocks ofthe olefin monomer feedstock is less than 20% by weight.
 15. The processof any preceding claim, wherein an amount of decene in any of firstand/or second feedstocks of the olefin monomer feedstock is less than10% by weight.
 16. The process of any preceding claim, wherein an amountof decene in any of first and/or second feedstocks of the olefin monomerfeedstock is less than 5% by weight.
 17. The process of any precedingclaim, further comprising oligomerizing the olefin monomer feed underconditions to at least partially isomerize the dimers, trimers, andhigher oligomers.
 18. The process of any preceding claim, wherein theunreacted monomer is distilled from the unsaturated oligomers andrecycled in a subsequent oligomerization reaction.
 19. The process ofany preceding claim, wherein isomerizing of the oligomer product isperformed in the absence of hydrogen.
 20. The process according to anypreceding claim, wherein an amount of cracked byproducts generatedduring isomerizing of the oligomer product is less than 10%.
 21. Theprocess according to any preceding claim, wherein an amount of crackedbyproducts generated during isomerizing of the oligomer product is lessthan 5%.
 22. The process according to any preceding claim, wherein anamount of cracked byproducts generated during isomerizing of theoligomer product is less than 1%.
 23. The process according to anypreceding claim, wherein isomerizing of the oligomer product isperformed at a temperature in the range of from 125° C. to 300° C., anda pressure in the range of from 1 PSI to 100 PSI of inert gas, in thepresence of an acid catalyst selected from the group consisting of solidmetals or metal oxides or their mixture of Group IVB, VB, VIB and Groupmetal oxides or mixed oxides of Group IIA to VA; mixed metal oxidescomprising WO_(x)/ZrO₂ type catalyst; solid natural or syntheticzeolites; and layered material, crystalline or amorphous material ofsilica, alumina, silicoaluminate, aluminophosphate, aluminumsilicophosphate.
 24. The process according to any preceding claim,wherein the dimer portion of the isomerized oligomer product isseparated by distillation from the isomerized oligomer product.
 25. Theprocess of any preceding claim where the oligomerization reaction iscarried out at a temperature range from 10-110° C.
 26. The process ofany preceding claim, wherein the oligomerization catalyst is selectedfrom the group consisting of zeolites, Friedel-Crafts catalysts,Bronsted acids, Lewis acids, acidic resins, acidic solid oxides, acidicsilico aluminophosphates, Group IVB metal oxides, Group VB metal oxides,Group VIB metal oxides, hydroxide or free metal forms of Group VIIImetals, and any combination thereof.
 27. The process of any precedingclaim, wherein the oligomerization reaction catalyst is BF₃, and thepromoter is an alcohol and/or an ester.
 28. The process of any precedingclaim, wherein the oligomerization is carried out in at least onecontinuously stirred reactor under oligomerization conditions with anaverage residence time of 60 to 400 minutes.
 29. The process of anypreceding claim, wherein the oligomerization is carried out in at leastone continuously stirred reactor under oligomerization conditions withan average residence time of 90 to 300 minutes.
 30. The process of anypreceding claim, wherein the oligomerization is carried out in at leastone continuously stirred reactor under oligomerization conditions withan average residence time of 120 to 240 minutes.
 31. The process of anypreceding claim, wherein the acid catalyst used for isomerizing theunsaturated polyolefin is a zeolite having a Constraint Index of about 2to about
 12. 32. The process of any preceding claim, wherein the acidcatalyst used for isomerizing the unsaturated polyolefin is a zeolitecontaining one or more Group VI B to VIII B metal elements.
 33. Theprocess of any preceding claim, wherein the pour point of theisomerization product is at least −9° C. less than that of the oligomerproduct prior to isomerization.
 34. The process according to anypreceding claim, wherein the pour point of the isomerization product isat least −15° C. less than that of the oligomer product prior toisomerization.
 35. The process according to any preceding claim, whereinthe pour point of the isomerization product is at least −21° C. lessthan that of the oligomerization product prior to isomerization.
 36. Theprocess according to any preceding claim, wherein the dimer product ofthe saturated hydrocarbon base oil has <5 wt % naphthalenes afterisomerization and hydrogenation.
 37. The process according to anypreceding claim, wherein the dimer product of the saturated hydrocarbonbase oil has <2.5 wt % naphthalenes after isomerization andhydrogenation.
 38. The process of any preceding claim, wherein the dimerproduct of the saturated hydrocarbon base oil has <1 wt % naphthalenesafter isomerization and hydrogenation.
 39. The process of any precedingclaim, wherein a percent yield of isomerized dimers produced in theisomerization is >90 wt. %.
 40. The process according to any precedingclaim, wherein a percent yield of isomerized dimers produced in theisomerization >95 wt. %.
 41. The process according to any precedingclaim, wherein a percent yield of isomerized dimers produced in theisomerization >97.5 wt. %.
 42. The process according to any precedingclaim, wherein a percent yield of isomerized dimers produced in theisomerization is >99 wt. %.
 43. The process according to any precedingclaim, wherein the base oil has a kinematic viscosity of measured at100° C. by ASTM D445 of 3.7 cSt to 4.8 cSt.
 44. The process according toany preceding claim 1, wherein the base oil has a kinematic viscosity ofmeasured at 100° C. by ASTM D445 of 3.8 cSt to 4.5 cSt.
 45. The processaccording to any preceding claim, wherein the saturated base oil has aViscosity Index 125 or greater.
 46. The process according to anypreceding claim, wherein the saturated base oil has a Viscosity Index130 or greater.
 47. The process according to any preceding, wherein thebase oil has a Viscosity Index 135 or greater.
 48. The process accordingto any preceding claim, wherein the base oil has a Viscosity Index 140or greater.
 49. The process according to any preceding claim, whereinthe base oil has a Viscosity Index of 150 or greater.
 50. The processaccording to any preceding claim, wherein the base oil has a CCS at −35°C. less than 1800 cP.
 51. The process according to any preceding claim,wherein the base oil has a CCS at −35° C. less than 1700 cP.
 52. Theprocess according to any preceding claim, wherein the base oil has a CCSat −35° C. less than 1600 cP.
 53. The process according to any precedingclaim, wherein the base oil has a CCS at −35° C. less than 1500 cP. 54.The process according to any preceding claim, wherein the base oil has aCCS at −35° C. less than 1400 cP.
 55. The process according to anypreceding claim, wherein the base oil has a CCS at −35° C. less than1300 cP.
 56. The process according to any preceding claim, wherein thebase oil has a CCS at −35° C. less than 1200 cP.
 57. The processaccording to any preceding claim, wherein the base oil has a CCS at −35°C. less than 1100 cP.
 58. The process according to any preceding claim,wherein the base oil has a Noack volatility less than 14%.
 59. Theprocess according to any preceding claim, wherein the base oil can becharacterized by a Noack volatility of less than 13%.
 60. The processaccording to any preceding claim, wherein the base oil can becharacterized by Noack volatility of less than 12%.
 61. The processaccording to any preceding claim, wherein the base oil can becharacterized by Noack volatility of less than 11%.
 62. The processaccording to any preceding claim, wherein the base oil can becharacterized by Noack volatility of less than 10%.
 63. The processaccording to any preceding claim, wherein the base oil can becharacterized by Noack volatility of less than 9%.
 64. The processaccording to any preceding claim, wherein the base oil can becharacterized by Noack volatility of less than 8%.
 65. The processaccording to any preceding claim, wherein the base oil can becharacterized by Noack volatility of less than 7%.
 66. The processaccording to any preceding claim, wherein the base oil can becharacterized by Noack volatility of less than 6%.
 67. The processaccording to any preceding claim, wherein the base oil can becharacterized by pour point of less than −27° C.
 68. The processaccording to any preceding claim, wherein the base oil can becharacterized by pour point of less than −30° C.
 69. The processaccording to any preceding claim, wherein the base oil can becharacterized by pour point of less than −33° C.
 70. The processaccording to any preceding claim, wherein the base oil can becharacterized by pour point of less than −36° C.
 71. The processaccording to any preceding claim, wherein the base oil can becharacterized by pour point of less than −39° C.
 72. The processaccording to any preceding claim, wherein the base oil can becharacterized by pour point of less than −42° C.
 73. The processaccording to any preceding claim, where a catalyst provided duringisomerization is other than a catalyst provided during oligomerization.